The six largest Arctic rivers (Yenisey, Lena, Ob’, Kolyma, Yukon, and Mackenzie) drain the organic-rich Arctic watersheds and serve as important pools in the global carbon cycle. Satellite remote sensing data are considered to be a necessary supplement to the ground-based monitoring of riverine organic matter circulation, especially for the ice-free periods in high-latitudes. In this study, we propose a remote sensing retrieval algorithm to obtain the chromophoric dissolved organic matter (CDOM) levels of the six largest Arctic rivers using Sentinel-2 images from 2016 to 2018. These CDOM results are converted to dissolved organic carbon (DOC) concentrations using the strong relationship (R2 = 0.89) between the field measurements of these two water constituents. The temporal-spatial distributions of the DOC in the six largest Arctic rivers during ice-free conditions are depicted. The performance of the retrieval algorithm verifies the capacity of using Sentinel-2 data to monitor riverine DOC variations due to its improved spatial resolution, better band placement, and increased observation frequency. River discharge, watershed slopes, human activities, and land use/land cover change drove much of the variation in the satellite-derived DOC. The seasonality, geography, and scale would affect the correlation between DOC concentration and these influence factors. Our results could improve the ability to monitor DOC fluxes in Arctic rivers and advance our understanding of the Earth’s carbon cycle.